CN102245739A

CN102245739A - Counter-current process for biomass conversion

Info

Publication number: CN102245739A
Application number: CN2009801500280A
Authority: CN
Inventors: P·欧康纳; S·达阿蒙
Original assignee: Kior Inc
Current assignee: Inaeris Technologies LLC
Priority date: 2008-12-10
Filing date: 2009-12-10
Publication date: 2011-11-16
Also published as: CA2744742A1; EP2376596A4; WO2010068809A1; US20110258912A1; BRPI0922854A2; EP2199364A3; EP2376596A1; EP2199364A2

Abstract

A countercurrent process is disclosed for converting solid biomass material. The solid biomass material travels through a reactor system in countercurrent with hot heat carrier materials, such as particulate heat earner material and hot gases. The solid biomass material is subjected to a first conversion at a first temperature T 1. and a second conversion at a second temperature, T 2, such that T 2 is higher than T 1. Bio-oil produced to at T J is not exposed to the higher temperature T 2. As a result, secondary reactions of the bio-oii components are minimized.

Description

The counter-current process of Wood Adhesives from Biomass

Background of invention

1. invention field

The present invention relates generally to conversion of biomass material, more specifically, relate to biological material and be catalytically converted into liquid feul.

2. association area is described

Having proposed several thermal cracking processes is used for conversion of biomass material is become liquid state or gaseous product.It is generally acknowledged that particularly liquid thermo-cracking product (often being called bio oil) is unsettled.For this reason, importantly make bio oil not contact the temperature of rising as far as possible.

Used during fast thermal cracking miscellaneous has been proposed.These process common principal characters are as follows: biological material is introduced thermal reaction chamber, wherein comprise or do not comprise particulate state thermal barrier material.If use the thermal barrier material, this material can be inert material, catalytic material or both combinations.Vaporize and the gasiform reaction product by volume displaced removing from reaction chamber with rare gas element.Vaporization reaction product and gaseous reaction products are entrained in the inert gas, arrive condensing chamber, and wherein the vaporization reaction product is condensed into liquid state, separate from inert gas and gaseous reaction products.

Though the time that reaction product stops in reaction chamber quite short (many authors propose the residence time be shorter than for 1 second), reaction product is still kept at high temperature before arriving condensing chamber.Therefore, unsettled bio oil composition has sizable chance generation secondary reaction.In order to obtain acceptable yields, reactor remains on or usually near under 500 ℃ the high temperature.This fact has increased the weight of this problem.

Therefore, need a kind of conversion process of biological material especially, wherein the reaction product of the conversion reaction contact pyritous time is compared with the used during fast thermal cracking of prior art and is shortened.

Summary of the invention

The counter-current process of the catalyzed conversion of the present invention by a kind of biological material is provided solves these problems, and described process comprises step:

(i) provide solid granulates shape biological material;

(ii) biological material is heated to first temperature T 1;

(iii) make biological material and hot gas and/or scorching hot particulate state thermal barrier material counter current contact, thereby second temperature T 2, the wherein T2＞T1 is provided.

Another aspect of the present invention is the bio oil that this counter-current process produces.

Brief Description Of Drawings

The features and advantages of the present invention can further be understood according to following accompanying drawing, wherein:

Fig. 1 is the unitary synoptic diagram of the fast pyrolysis of prior art;

Fig. 2 is the synoptic diagram of first kind of embodiment of process of the present invention.

Fig. 3 is the synoptic diagram of variant of the embodiment of Fig. 2;

Fig. 4 is the synoptic diagram of second kind of embodiment of process of the present invention.

Fig. 5,6, the 7th, the synoptic diagram of the independent embodiment of process of the present invention.

Detailed Description Of The Invention

The present invention relates to a kind of counter-current process of catalyzed conversion of biological material, described process comprises step:

(i) provide solid granulates shape biological material;

(ii) biological material is heated to first temperature T 1;

A main aspect of the present invention is that the integral part of Wood Adhesives from Biomass reaction takes place under lesser temps T1, and the reaction product that forms under this temperature does not contact comparatively high temps T2.The biological material that does not transform under lesser temps T1 contacts comparatively high temps T2 then, with further conversion.The common poor 50-200 of T1 and T2 ℃.

In one embodiment of the invention, step (ii) comprises solid granulates shape biological material and scorching hot thermal barrier material mixing.Step (ii) with this process in the later stage, coke and/or deposition of carbon are on the thermal barrier material.In a preference, coke and deposition of carbon are burnouted from particulate state thermal barrier material in interchanger.The essential reaction heat of thermal barrier material is provided with the coke and the charcoal combustion heat.

Particulate state thermal barrier material can be an inert material, and is for example husky, maybe can be catalytic material.Term used herein " catalytic material " refers to a kind of material, and its existence in reaction zone influences at least one conversion reaction parameter, productive rate and product and distributes, and itself is not by reaction consumes.

The example of catalytic material comprises salt, oxide compound and the oxyhydroxide of basic metal and alkaline-earth metal, aluminum oxide, and aluminosilicate, clay, hydrotalcite and hydrotalcite sample material are from the ashes of Wood Adhesives from Biomass reaction etc.Also can use this type of mixtures of material.

Term used herein " hydrotalcite " the formula Mg that refers to see service ₆Al ₂(CO ₃) (OH) ₁₆XH ₂The hydroxyl carbonate of O, wherein x normally 4.Term " the hydrotalcite sample material " formula M (II) that refers to see service ₆M (III) ₂(CO ₃) (OH) ₁₆XH ₂The material of O, wherein M (II) is a divalent-metal ion, and M (III) is a trivalent metal ion.These materials and hydrotalcite itself have identical main crystalline nature.

The particulate biomass material can with catalyzer step (ii) before, step (ii) during or step (ii) before with during contact.For example, if catalyzer is a water-soluble material, promptly under the situation of basic metal and alkaline earth metal compound, the catalyzer solvent that can be soluble in the aqueous phase can flood biological material with aqueous catalyst solution before (ii) in step.

Catalyzer can be a particle form.The particulate state solid catalyst can

With the particulate biomass material step (ii) before, in an independent mechanical treatment step, contact.Such mechanical treatment can comprise the milling of particulate biomass material and particulate state catalytic material mixture, grinds, kneading etc.

The catalytic material of particulate solid form can be contacted during step (ii) with the particulate biomass material.In a preference, the thermal barrier material comprises or is made up of the particulate state solid catalyst.

Charcoal and sedimentation of coke are on particulate state thermal barrier material.The inorganic substance that are present in the particulate biomass parent material change into ash content in conversion reaction.Process of the present invention produces solid byproducts, and it mainly is made up of particulate state thermal barrier material, and this material can comprise, or by solid catalyst material, coke, charcoal and ash composition.Though charcoal itself can be a liquid, in the time of on being deposited on the particulate state solid-state material, it is considered to the solid byproducts of process.

In a preference, these solid byproducts experience high temperature and oxygen-containing atmosphere (for example air) in interchanger.

Charcoal and coke can be burned, and the heat of generation is used to improve the temperature of thermal barrier material.This heat is transmitted back process of the present invention.

The principal reaction product of process is the liquid of vaporization, i.e. condensable gas, and gaseous reaction products.Condensable gas and gaseous reaction products are entrained in the step hot gas (iii) and arrive first condensing chamber, wherein change into liquid to the small part condensable gases.

Burn the generation hot waste gas from the uncondensable gaseous combustible that condensing chamber is overflowed.Hot waste gas can be used as hot gas, and it contacts with biological material in (iii) in the step of process.Excessive heat from this combustion processes can be used for the heat hot solid support material.Waste gas from interchanger also can be used as hot gas, and it contacts in (iii) in the step of process with biological material.

It is desirable to provides the hot gas with reduced form in step in (iii).This can pass through to handle the burning of interchanger and/or non-condensable gases, thereby produces the waste gas that contains significant quantity carbon monoxide (CO).General CO produces when the oxygen of substoichiometric amount burns at carbonaceous material.

It is desirable to can be by adding hydrogen donor gas, and for example methane or other hydro carbons further improve the reductibility that is used for step hot gas (iii).

Process of the present invention can be carried out at least two reactor cascades,

Wherein first reactor is used for step (ii).First reactor can be swirling flow, and wherein biological particles contacts at a high speed with the solid state heat carrier granule.

Suitable temp in first reactor maintains 200-450 ℃, and preferred 300-400 ℃, more preferably 320-380 ℃.

In another embodiment, process is carried out in the descending bed of adverse current (air lift type (gas-up)) (downer), and it is a vertical tube, and wherein the particulate state solid matter runs to the bottom from the top, and mobile hot gas is countercurrent direction with making progress.The temperature range of pipe bottom is 450-550 ℃, preferred 480-520 ℃.Near the pipe top temperature range is 250-350 ℃.

Embodiment

Described some embodiments of the present invention below with reference to accompanying drawing, it only is used for for example.According to Fig. 1, synoptic diagram has shown the fast pyrolysis unit 100 of representing the prior art process.Particulate state solid-state biomass 115 is introduced into reactor 110, and it maintains required invert point, reaches usually or near 500 ℃.Rare gas element 116, for example water vapour, nitrogen or water vapour/nitrogen mixture are introduced into reactor 110, and to carry gaseous reaction products 111 secretly to condensing chamber 150, wherein condensable gases is converted into liquid bio oil 152.Never isolate bio oil in the condensable gas 151, deliver to tank 170.

Come the solid and the charcoal 112 of autoreactor 110 to be admitted to interchanger 140, contact with air 113.Normally about 650 ℃ of temperature in the interchanger 140.Waste gas 141 mainly is CO ₂Scorching hot thermal barrier particle 142 from interchanger 140 is recovered into reactor 110.

In the time of in also being present in reactor 110, the temperature of reaction of reaction product contact reaches or near 500 ℃.Even after arriving condensing chamber 150, also need certain hour that the temperature of reaction product is reduced to below 350 ℃.Therefore, reaction product experience secondary reaction, the quality of infringement bio oil 152.

Fig. 2 has shown a specific embodiment of the present invention.

Unit 200 comprises a mechanical treatment reactor 210, the first conversion reactors 220, the second conversion reactors 230, interchanger 240, the first condensing chambers 250 and second condensing chamber 260.

Mixing solid phase grain biomass and solid granulates shape catalyzer, and in mechanical treatment reactor 210 mechanical treatment.Mechanical treatment can be grinding, mucous membrane, kneading etc.Should be understood that mechanical treatment will cause granules of catalyst to contact with the close of biological particles.As needs, mechanical treatment reactor 210 can be operated under heating up, to realize the part drying of biomass.Temperature in the mechanical treatment reactor 210 can maintain in envrionment temperature to the 200 ℃ scope, preferred 80-150 ℃.Granules of catalyst provides heat, and it makes that the temperature of interchanger 240 is very high.Particularly, if mechanical treatment reactor 210 when the operation of the upper limit of described temperature range, some Wood Adhesives from Biomass may take place.The gaseous product of discharging from mechanical treatment reactor 210 is transported to second condensing chamber 260, wherein uncondensable gaseous product is separated with condensable steam (mainly being water).

Biomass/catalyst mixture is transferred to first conversion reactor 220 from mechanical treatment reactor 210.First conversion reactor 220 is between 200-450 ℃, and is more typical between 300-400 ℃, preferably 350 ℃ or near operation.Extra heat catalyzer by interchanger 240 and provide heat from the hot gas of second conversion reactor 230.

Significant Wood Adhesives from Biomass takes place in first conversion reactor 220.The reaction product that contains condensable gases and non-condensable gases is transferred to first condensing chamber 250.Uncondensable gas can be used as thermal source.In case liquefaction, the gas of condensation forms high-quality bio oil.It is desirable to, the oxygen level of this bio oil is lower than 25wt%, preferably is lower than 15wt%, and always acid number (TAN) is lower than 30, preferably is lower than 10.Importantly the reaction product of first conversion reactor 220 never " runs into " service temperature that is higher than first conversion reactor 220, for example 350 ℃ temperature.This temperature is more much lower than reaction product contacted in the prior art thermo-cracking unit of Fig. 1 500 ℃.Should be understood that owing to this temperature contrast the bio oil that produces in first conversion reactor 220 of Fig. 2 has significantly better quality than the bio oil that produces in Fig. 1 reactor 110.

Solid from first conversion reactor 220 is transferred to second conversion reactor 230.These solids are mainly by unconverted biomass; The solid-state biomass reaction product comprises coke and charcoal; Granules of catalyst; And ash composition.

Temperature in second conversion reactor 230 maintains 400-550 ℃ usually, and is more typical in 450-520 ℃ scope.Compare with first conversion reactor 220, this higher temperature causes biomass further to transform, thereby guarantees acceptable bio oil productive rate.Though what produce in bio oil mass ratio first conversion reactor 220 that produces in second conversion reactor 230 is poor, the oeverall quality of bio oil than whole conversion all under comparatively high temps, carry out good.

Provide heat from the hot gas 241 of interchanger 240 with from 242 pairs second conversion reactors 230 of thermocatalyst of interchanger 240.Reaction product from second conversion reactor 230 is transferred to first conversion reactor 220 as hot gas 231.Alternative, if come the air-flow of

autoreactor

220 and 230 need keep independent, can be sent to the 3rd condensing chamber (not shown) from the reaction product of second conversion reactor 230.In this case, the heat of reactor 220 is to be provided by thermocatalyst 232 fully.

Solid from second conversion reactor 230 is transferred to interchanger 240.These solids are mainly by coke, charcoal, granules of catalyst and ash composition.By oxygen-containing gas 243 is provided, air for example, coke and charcoal burnout in interchanger 240.As shown in Figure 2, if the thermal equilibrium requirement of process also can be burnt in interchanger 240 from the gaseous product of process.In most of the cases, interchanger 240 coke that can obtain and charcoal amount are than the many of required process heat enough are provided.

May it is desirable to operation interchanger 240 under the oxygen condition of substoichiometric amount, thereby make hot gas 241 contain the carbon monoxide of significant quantity (CO).Carbon monoxide has reductibility, and it is useful for the Wood Adhesives from Biomass process.Similarly, can operate interchanger 240, make on thermocatalyst 222,232 and 242, to have residual coke.Residual coke is given reaction mixture in each reactor with reductibility.

In addition, from the hydrocarbon gas of

condensing chamber

250 and 260 can injection process one or more reactors, thereby hydrogen donor is provided in reaction mixture.The oxygen level of each bio oil that produces in can both the reduction process in these means.

Fig. 3 has shown the synoptic diagram of the variant of embodiment shown in Figure 2.Unit 300 comprises mechanical treatment reactor 310, the first condensing chambers 350 and second condensing chamber 360.Shown in the embodiment of Fig. 2, interchanger 340 produces hot gas 341 and scorching hot particulate state thermal barrier material 322.

In this variant, pass through catalytic cracking unit 380 from the reaction product of second conversion reactor 330.Catalyzer essence in the catalytic cracking unit 380 is tart.Suitable example comprises acid zeolite, for example HZSM-S.Cracking reaction takes place in catalytic cracking unit 380, further improves the quality of bio oil 370.Hot gas 331 from second conversion reactor 330 is admitted to catalytic cracking unit 380.

Fig. 4 has shown another embodiment of process of the present invention.Unit 400 comprises the descending bed 430 of adverse current, and wherein gas moves upward, and solid moves downward.Biological particles 431 is with send into descending bed from the top from the hot catalyst particles 432 of interchanger 440.The operation of descending bed 430 reaches the temperature of its bottom or near 500 ℃; The temperature at its top is for being lower than 350 ℃, for example 300 ℃.Hot gas 434 and thermocatalyst 432 are to 430 heat supplies of descending bed.

Near descending bed 430 tops, collect the liquid reaction product of gaseous state and vaporization, and transfer to condensing chamber 450.Bio oil from condensing chamber 450 is stored in the jar 470.From the gaseous product 451 of condensing chamber 450 be transferred to interchanger 440 after air-flow 452 mixes.

Solid residue mainly is made up of granules of catalyst, ash content, coke and charcoal, is collected in stripping tower 480.From the solid residue of stripping tower 480, remove volatile reaction product with the rare gas element (not shown).Stripping tower 480 can be used the thermocatalyst heating from air-flow 434.Coke and charcoal on coke and the charcoal solid granulates that burnouts in interchanger 440.

Ash content can separate from the solid catalyst particle that leaves interchanger 440.Can use ash content outside process, for example as fertilizer sources perhaps is ground into required particle diameter, is recovered into process, for example mixes with thermocatalyst 432.

Fig. 5 has shown that the present invention adapts to the synoptic diagram of the embodiment of water Wood Adhesives from Biomass.Unit 500 comprises the descending bed 530 of adverse current (gas makes progress, and solid is downward).The water biomass are grown in pond 510.Ideally, the water biomass are grown on mineral precipitation so that subsequently with water sepn.

Moistening water biomass from pond 510 are transferred to strainer 520, remove most of water.The water biomass are transferred to dry reactor 540 from strainer 520, its maintain 100 ℃ or near, to remove most of remainder water.Steam condensation in first condensing chamber 550 from dry reactor 540.Liquid water from condensing chamber 550 is stored within the storage tank 560.Quality from the water of first condensing chamber 550 is enough to be used in irrigating and family expenses, even is used for culinary art and drinks.

Drying water biomass from dry reactor are admitted to descending bed 530 tops.Biomass move down in descending bed 530, and with hot gas 571 adverse currents from interchanger 570, the latter is admitted to descending bed at stripping tower 580 places.

Handle descending bed 530, make bottom temp for reaching or near 450 ℃, head temperature is for reaching or near 300 ℃.Should be understood that the water biomass do not contain or contain seldom xylogen usually, can under than the lower temperature of the process of embodiment mentioned above, transform.

The required heat of descending bed 530 is by being provided by dry reaction chamber 540 on hot gas 571 and the less degree, and the latter heats biomass and mineral grain to about 100 ℃ temperature.If desired, can provide extra heat by the scorching hot mineral grain 572 of part being transported to descending bed 530 tops.

As shown in the figure, the hot mineral grain from interchanger 570 cools off in heat exchanger 575.The heat that reclaims from mineral grain can offer for example dry reaction chamber 540, descending bed 530 or pond 510.

The mineral grain 573 that leaves interchanger 575 can be recycled in the growth pond 510.Part mineral grain 573 can be sent in the storage tank 515, and it contains the water from strainer 520.Mineral grain is caught the organic residue that is present in the storage tank 515.515。The mineral grain of carrying organic matter is recyclable goes into strainer 520 or dry reaction chamber 540.

Gaseous state and vaporization liquid reaction product from descending bed 530 are sent to second condensing chamber 535, and wherein gasifying liquid is condensed into bio oil 591, and it is sent to storage tank 590.

Fig. 6 has shown the synoptic diagram of another embodiment of process of the present invention.Unit 600 comprises upstream injection bed reaction chamber 630.Particulate biomass 610 can randomly be sent into reactor 630 with the thermocatalyst 615 from interchanger 640 at the top.

Hot gas 671 from interchanger 640 is admitted to reactor 630 bottoms.Gaseous state and vaporization reaction product 631 are transferred to condensing chamber 650, and wherein the vaporization reaction product is liquefied as bio oil 651, and it is stored within the storage tank 670.Gaseous reaction products 652 mixes with air 653, sends into interchanger 640.

Fig. 7 has shown the synoptic diagram of another embodiment of process of the present invention.Unit 700 comprises helical reactors 730.Biomass 710 are admitted to the A district of helical reactors 730 with thermal barrier particle 715.Handle screw rod, make biological particles and thermal barrier particle move, with hot gas 741 adverse currents from interchanger 740 from the A district to B district direction.The operation of spiral response chamber make the A district maintain 300 ℃ or near, and the B district maintain 500 ℃ or near.Thermal barrier particle 715 and hot gas 741 are to reaction chamber 730 heat supplies.

Gaseous state and gasifying liquid reaction product are transferred to condensing chamber 750, and wherein the gasifying liquid product is condensed into bio oil 751, and it is admitted to storage tank: 770.

Gaseous reaction products 752 from condensing chamber 750 mixes with air 753, sends into interchanger 740.

Collect in separator 780 from the solid of spiral response chamber 730, wherein solid is divided into the thermal barrier particle gas 782 of charcoal/ash stream 781 and load coke.The latter regenerates in interchanger 740.

Claims

1. the counter-current process of a catalyzed conversion biological material, described process comprises step:

(i) provide solid granulates shape biological material;

(ii) biological material is heated to first temperature T 1;

2. process as claimed in claim 1 is characterized in that, described step (ii) comprises solid granulates shape biological material and scorching hot thermal barrier material mixing.

3. process as claimed in claim 1 or 2 is characterized in that, step (ii) before or during, solid granulates shape biological material contacts with catalyzer.

4. process as claimed in claim 3 is characterized in that, described catalyzer is a solid granulates shape form.

5. process as claimed in claim 4 is characterized in that, described thermal barrier material comprises solid granulates shape catalyzer.

6. process as claimed in claim 5 is characterized in that, reclaims solid state reaction by product and solid granulates shape mixture of catalysts from reaction mixture.

7. process as claimed in claim 6 is characterized in that, also comprises the step of separate solid pellet type catalyst from the solid state reaction by product.

8. as the described process of previous arbitrary claim, it is characterized in that, also comprise: collect the step of gaseous reaction products, described reaction product comprises condensable and condensable gases and condensable gases is changed into the step of liquid in first condensing chamber not.

9. process as claimed in claim 8 is characterized in that, also comprises the not step of condensable gases of burning at least a portion.

10. process as claimed in claim 9 is characterized in that, described burning at least a portion heat that condensable gases did not produce is used to the heat hot solid support material.

11., it is characterized in that described burning at least a portion at least a portion waste gas that condensable gases did not produce is used as the hot gas of step in (iii) as claim 9 or 10 described processes.

12. process as claimed in claim 11 is characterized in that, in swirling flow from thermal barrier material separation waste gas.

13., it is characterized in that described waste gas comprises CO as claim 11 or 12 described processes.

14. the described process of as above arbitrary claim is characterized in that, wherein carries out this process at least in the cascade of two reactors.

15. process as claimed in claim 14 is characterized in that, wherein first of reactor dosage is swirling flow.

16. process as claimed in claim 15 is characterized in that, in first reactor, biological particles is to contact with the solid state heat carrier granule at a high speed.

17., it is characterized in that described first reactor is preferably operated at 100-180 ℃ as claim 15 or 16 described processes in 100-150 ℃ temperature range.

18., it is characterized in that this process is carried out at least in the series of two vertical reaction tube devices as each described process among the claim 1-13.

19., it is characterized in that this process is carried out in the adverse current helical reactors as each described process among the claim 1-13.

20., it is characterized in that this process is carried out as each described process among the claim 1-13 in a series of vertical reaction tube devices.

21. a device that carries out each described process among the claim 1-13, this device comprise first reactor of operating under (i) temperature in 100-180 ℃ of scope, wherein biological particles mixes with granules of catalyst; (ii) second reactor of in 250-400 ℃ of temperature range, operating; The 3rd reactor of in 400-550 ℃ of temperature range, operating.